CA2065464C - Austenitic nickel-chromium-iron alloy - Google Patents
Austenitic nickel-chromium-iron alloy Download PDFInfo
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- CA2065464C CA2065464C CA002065464A CA2065464A CA2065464C CA 2065464 C CA2065464 C CA 2065464C CA 002065464 A CA002065464 A CA 002065464A CA 2065464 A CA2065464 A CA 2065464A CA 2065464 C CA2065464 C CA 2065464C
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- iron alloy
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- 229910000640 Fe alloy Inorganic materials 0.000 title claims abstract description 11
- BIJOYKCOMBZXAE-UHFFFAOYSA-N chromium iron nickel Chemical compound [Cr].[Fe].[Ni] BIJOYKCOMBZXAE-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 239000010936 titanium Substances 0.000 claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004411 aluminium Substances 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 10
- 239000011651 chromium Substances 0.000 claims abstract description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 8
- 239000011777 magnesium Substances 0.000 claims abstract description 8
- 239000010955 niobium Substances 0.000 claims abstract description 8
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 8
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 8
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 7
- 239000011575 calcium Substances 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 238000002844 melting Methods 0.000 claims abstract description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 239000011572 manganese Substances 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- 230000008018 melting Effects 0.000 claims abstract description 4
- 239000012535 impurity Substances 0.000 claims abstract description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- 239000005864 Sulphur Substances 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 6
- 229910045601 alloy Inorganic materials 0.000 description 37
- 239000000956 alloy Substances 0.000 description 37
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000007792 addition Methods 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- -1 titanium nitrides Chemical class 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 208000019300 CLIPPERS Diseases 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910000604 Ferrochrome Inorganic materials 0.000 description 1
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- 229910001005 Ni3Al Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- IHNDUGMUECOVKK-UHFFFAOYSA-N aluminum chromium(3+) oxygen(2-) Chemical compound [O-2].[Cr+3].[O-2].[Al+3] IHNDUGMUECOVKK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 208000021930 chronic lymphocytic inflammation with pontine perivascular enhancement responsive to steroids Diseases 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Heat Treatments In General, Especially Conveying And Cooling (AREA)
- Heat Treatment Of Steel (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
Abstract
The invention relates to an austenitic-chromium-iron alloy and its use as a material for articles with high resistance to isothermal and cyclic high temperature oxidation, high heat-resistance and high creep rupture strength at temperatures above 1100 to 1200°C.
The characterizing feature of the invention is that the austenitic nickel-chromium-iron alloy consists (in % by weight) of:
0.12 to 0.30 % carbon 23 to 30 % chromium 8 to 11 % iron 1.8 to 2.4 % aluminium 0.01 to 0.15 % yttrium 0.01 to 1.0 % titanium 0.01 to 1.0 % niobium 0.01 to 0.20 % zirconium 0.001 to 0.015 % magnesium 0.001 to 0.010 % - calcium max 0.030 % nitrogen max 0.50 % silicon max 0.25 % manganese max 0.020 % phosphorus max 0.010 % sulphur residue nickel, including unavoidable impurities caused by melting.
The characterizing feature of the invention is that the austenitic nickel-chromium-iron alloy consists (in % by weight) of:
0.12 to 0.30 % carbon 23 to 30 % chromium 8 to 11 % iron 1.8 to 2.4 % aluminium 0.01 to 0.15 % yttrium 0.01 to 1.0 % titanium 0.01 to 1.0 % niobium 0.01 to 0.20 % zirconium 0.001 to 0.015 % magnesium 0.001 to 0.010 % - calcium max 0.030 % nitrogen max 0.50 % silicon max 0.25 % manganese max 0.020 % phosphorus max 0.010 % sulphur residue nickel, including unavoidable impurities caused by melting.
Description
Case 10227 03.04.91 VDM Nickel-Technologie AG, Werdohl AUSTENTTIC NICKEL-CHROMIUM-IRON ALLOY
The invention relates to an austenitic nickel-chromium-iron alloy and its use as a material for articles having high resistance to isothermal and cyclic high temperature oxidation, high resistance to heat and high creep rupture strength at temperatures above 1100 to 1200°C.
Articles such as furnace components, radiation tubes, furnace rollers, furnace muffles and supporting systems in kilns for ceramic products are not only loaded isothermally in operation at very high temperatures above 1000°C, but they must also withstand temperature loadings during the heating and cooling of the furnaces or radiation tubes.
They must therefore have outstanding scale resistance,. not only with isothermal, but also With cyclic-oxidation, and also have adequate resistance to heat and creep rupture strength.
US Patent Specification 3 607_243 disclosed for the first time an austenitic alloy having contents of (details in % by weight) up to 0.1o carbon, 58 - 63o nickel, 21 - 25% chromium, 1 - 1.7%
aluminium, and also optionally up to 0.5o silicon, up to 1.0%
manganese, up to 0.6o titanium, up to 0.006% boron, up to d..to magnesium, up to 0.05e calcium, residue iron, the phosphorus content being below 0.030e and the sulphur content below 0.015%:
The invention relates to an austenitic nickel-chromium-iron alloy and its use as a material for articles having high resistance to isothermal and cyclic high temperature oxidation, high resistance to heat and high creep rupture strength at temperatures above 1100 to 1200°C.
Articles such as furnace components, radiation tubes, furnace rollers, furnace muffles and supporting systems in kilns for ceramic products are not only loaded isothermally in operation at very high temperatures above 1000°C, but they must also withstand temperature loadings during the heating and cooling of the furnaces or radiation tubes.
They must therefore have outstanding scale resistance,. not only with isothermal, but also With cyclic-oxidation, and also have adequate resistance to heat and creep rupture strength.
US Patent Specification 3 607_243 disclosed for the first time an austenitic alloy having contents of (details in % by weight) up to 0.1o carbon, 58 - 63o nickel, 21 - 25% chromium, 1 - 1.7%
aluminium, and also optionally up to 0.5o silicon, up to 1.0%
manganese, up to 0.6o titanium, up to 0.006% boron, up to d..to magnesium, up to 0.05e calcium, residue iron, the phosphorus content being below 0.030e and the sulphur content below 0.015%:
this alloy has particularly nigh resistivity, more particularly to cyclic axidation at temperatures up to 2000°F (1093°C).
The heat resistance values are stated as follows 80 MPa for 1800°F, 45 MPa for 2000°F and 23 MPa for 2100°F.
After 1000 hours the creep rupture strength was 32 MPa for 1600°F, 16 MPa for 1800°F and 7 MPa for 2000°F. Material NiCr23Fe (Material No. 2.4851 and UNS Designation N 06601), which lies within these alloying limits, was introduced for industrial use on that basis. The material proves its usefulness above all when applied in the temperature range above 1000°C. This is due to the formation of a protective layer of chromium oxide-aluminium oxide, but more particularly to the overall low tendency of 'the oxide layer to peel. off under alternating temperature loadings. The material. has therefore been developed into an important material in industrial furnace construction.-Typical applications are radiation tubes for gas-heated furnaces and conveying rollers in roller hearth furnaces for ceramic products. Moreover, the rnaterial.is also suitable for parts of waste gas detoxification installations and petrochemical plants.
To further enhance the properties decisive for the use of this material for utilization temperatures above 1100 to 1200°C, according to US Patent Specification 4 784 830 nitrogen in quantities of 0.04 to 0.1o by weight are added to the material known from US Patent Specificat~.on 3 607 243, while at the same time a titanium content of 0.2 to l.Oa is compulsory.
Advantageously the silicon content should also be above 0.25% by weight and so correlated with the titanium content as to obtain a Si:Ti ratio of 0.85 to 3Ø The chromium contents are 19 - 23a, the aluminium contents being 0.75 - 2.00, with nickel contents of 55 - 65%.
By these steps an improvement in resistance to oxidation with utilization temperatures up to 1200°C is achieved, something which enabled the service life of, for example, furnace rollers to be increased to 12 months and more, in comparison with 2 months in the case of furnace rollers made from the material disclosed in US Patent Specification 3 607 243. This improvement in the service life of furnace components is mainly due to a stabilization of the microstructure by titanium nitrides at temperatures of 1200°C. As described in US Patent Specification 3 607 243, the carbon content also must not exceed 0.1% by weight, to prevent the formation of carbides, more particularly of the type M23C6, since these have a disadvantageous effect on microstructure and on the properties of the alloy at very high temperatures.
However, not only resistance to oxidation (expressed by cyclic change in weight (g/mZ.h) in air at high test temperatures, e.g., 2000'f, as described in US.Patent Specification 4 784 830) is decisive for the. service life-of highly heat-resistant particles, but so are resistance to heat and creep rupture strength at the particular temperatures of utilization.
Tt is an object of the invention so to design, nickel-chromium-iron alloys of the kind specified that, accompanied by adequate resistance to oxidation, the values of heat resistance and creep rupture strength are impro.v~d, thus significantly increasing the service life of articles made from such alloys.
This problem is solved by an austenitic nickel-chromium-iron.alloy, consisting of (details in % by weight):
carbon . 0.12 to 0.30 %
chromium . 23 to 30 %
iron . 8 to 11 aluminium . 1.8 to 2.4' yttrium . 0.01 to 0.15 %
titanium . 0.01 to 1.0 %
niobium . 0.01 to 1.0 zirconium . 0.01 to 0.20 magnesium . 0.001 to 0.015 %
calcium. . 0.001 to 0Ø10 nitrogen . max 0.030 silicon . max 0.50 %
manganese . max 0.25 phosphorus . max 0.020 sulphur . - max 0.010 4 nickel . residue , including unavoidable impurities caused by melting.
~n a preferred variant of the alloy, the contents are as.follows:
carbon . 0.15 to 0.25 chromium . 24 to 26 %
aluminium . 2.1 to 2.4 yttrium . 0.05 to 0.12 0 titanium . 0.40 to 0.60 0 ;
niobium . 0.40 to 0.60 0 zirconium . 0.01 to 0.10 0 nitrogen . max 0.010 %.
with, unaltered ranges of content the t of the alloying of res elements.
The nickel-chromium-iron alloy according to the invention has carbon contents of 0.12 to 0.3% by weight, in contrast with the prior art, which~permits carbon contents only up to 0.100 by weight at the most, since it was believed that only such low carbon contents could ensure the required existence to oxidation at temperatures up to 1200°C.
Surprisingly, carbon contents of this order of magnitude in conjunction with the other additives provided according to the invention, mare particularly yttrium and zirconium, not only enhance heat resistance and creep rupture strength, but also improve, resistance to oxidation.
Since in the alloy according to the invention the nitrogen content is kept~as low as possible, the carbon contents according.
to the invention of 0.1.2 to 0.30% by weight, in conjunction with the stable carbide formers titanium, niobium and zirconium, produce essentially carbides of said elements which are thermally stable even at temperatures up to 1200°C. As a result, the formation of chromium carbides of the type Cr2gC6 is substantially prevented thereby. The result is that in the first place, the formation of the titanium, niobium and zirconium CarDldeS . ~.JCll.~f? Slave gr°_3tSr t er_?la1 StaD111t'T t an t a C.
rOmi'.131 Car'JlQeS ~ aSt_:.:?g! j l~:l~Y'.~~VeS reSlSLanC2 t0 ~ea~ aI'lC Crr°O r '~~::~5 , Strength, While in the Second place more ChrOmlum is avail3Jle fOZ"tile formation Of a prOteCtl.Ve Chromium oxide layer, SO that resistance to oxidation is improved with the simultaneous addition of yttrium and airconium.
Chromium contents of at least 23% by weigzt are rec_r'.:i red to ensure adeauate resistance to oxidation at temperatures of above 1200°C. The top limit should not exceed 30% by weight, to avoid problems in the hot working of the alloy.
Particularly in the temperature range betTaeen 600 and 800°C, which the material when used passes through both during heating and also cooling, aluminium improves resistance to heat by the precipitation of the phase Ni3Al (so-called '~ ' phase) . Since the preCipltation of this phase is at the same time connected with a drop in toughness, the aluminium contents must be limited to 1.8 to 2.~~ by we~g~.t.
The silicon content should be as lcw as possible, to avoid the formation of low-melting phases. The manganese content should not exceed O.zS% by weigt?t,~ to avoid negative ez'fec~s on the resistance to oxidation of the material.
Additions of magnesium and calcium improve hat workability and also enhance resistance to oxidation. However, the top limits of 0.025% by weight (magnesium) and 0.020% by weight (oalcium) should not be exceeded, since~magnesium and calcium contents ' .oove these limit values encourage the occurrence of low-melting phases and therefore lead to a deterioration in hot workability.
The iron contents of the alloy according to the invention lie in the range of 8 to llo by weight, these values being determined by the need to be able to use cheap ferrochrome and ferronickel in the melting of the alloy.
The advantages achieved by the alloy according to the invention will be explained in detail hereinafter. Table 1 takes the analyses of two alloys A and B according to the invention and a prior art alloy C, such as can be gathered from US Patent Specification 4 784 830.
Table 1 Allay A Alloy B ~ Alloy C
(contents stated in o by weight) carbon 0.18 0.18. 0.055 chromium 25.0 25.5 23.0 iron 11.0 10.0 14.0 aluminium 1.85 ~ 2.10 1.35 yttrium 0.06 0.11 titanium 0.15 0.59 0.45 niobium 0.01 0.59 zirconium 0.10 0.10 magnesium 0.008 ~ O.OOE
calcium 0.002 O.OOI
nitrogen 0.002 0.006 0.040 _8_ ~~~4~~
silicon 0.29 0.06 0.40 manganese 0.15 0,02 0.25 phosphorus 0.004 0.003 0.011 sulphur 0.003 0.002 0.004 nickel residue residue residue The material properties of these alloys form the subaect matter of Figs. 1 to 5, which show:
Ficx~~ for the alloys A, B and C
heat resistance Rm (MPa) in dependence on temperature (°C) Fic~. 2 for the alloys A, B and C
the 1o yield point Rp (MPa) in dependence on temperature (°G) F_iq. 3 for the alloys A and C
the to time yield limit Rp 1.0/10000 (MPa) after a time of 10000 hours in dependence on temperature (°C) Fib. ~4 for the alloys A and C
the creep rupture strength in dependence on temperature Rm/10000 (MPa) after a time of 10000 hours in dependence on temperature (°), and Fig. 5 for the alloys A and C
the cyclic resistance to oxidation in air (specific change in weight in g/m2.h) in dependence on temperature.(°C).
"'he -values plotted in dependence or. temperature in Fia. 1 for heat resistance and i n Fi a. 2 for th a 1% yiel d poi:,t are important characteristic values, indicating the extent to which the material can be loaded at a particular temperature.
It must be pared that over the whole temperature range in question of 850 to 1.200°C, the alloy according to the invention has distinctly higher values than the prior art alloy C as regards both heat resistance Rm and also the to yield point Rp.
Bven better values are achieved by the alloy B according to the invention, whose composition lies within the variant alloy set forth in claim 2. By this variant alloy both the heat resistance and also the yield point can be almost doubled up to temperatures of 1000 ° C.
Fia. 3 and Fia. 4 compare the creep rupture strength behaviour of the alloy A according to the invention with that of the prior art alloy C.
The creep rupture strength and the l~ time yield point were determined in the usual creep tests (cf. "Wet~kstoffkunde Stahl°', Vol. l, published by Springer Verlag, Berlin, 2984, pages 384 to 396 and DIN 5011.8).
Creep rupture strength (MFa) is taken to be a measurement of the capability of the material not to be destroyed by the effect of an operative load. The 1°s time yield point, which states the stress (in MPa) far a given loading time at which a to expax~sion is reached, characterizes the functional failure of material at a particular long-term loading for the 'temperature in question.
The alloy A according to the invention is clearly superior to the prior art alloy C over the whole temperature range both as regards creep rupture strength and also the 1o time yield point.
In comparison with the alloy C, the gain in strength of the alloy A according to the invention is more than 25~ at every temperature.
In Fib. 5 the cyclic resistance to oxidation determined in air for the alloys A and C are compared by plotting specific change in weight over temperature. As a rule increases in.weight (+) are desirable, since reductions in weight (-) are often an indication of heavily peeling scale.
For this reason the behaviour of the alloy A according to the invention must be considered superior to that of the prior art' alloy C, which intersects the abscissa (transition to loss in weight) as early as about 1000°C, while the alloy A passes through zero only at approximately 1050°C.
Due to its satisfactory properties at elevated temperatures, the nic3sel-chromium-iron alloy according to the invention is a preferred material for articles which must have a creep rupture strength (Rm/10000) of at least 5 MPa, accompanied by a la time yield paint (Rpl.O/10000) of at least 2 MPa and high resistance to oxidation in practical operation, referred to a temperature of 7.100°C and a loading duration of 10000 hours, such as, for examples - radiation tubes for the heating of furnaces - furnace rollers for the annealing of metal ox ceramic goads ~~~~4~~
- muffles for scaling furnaces, for example, for furnaces for the bright annealing of special quality steels - tubes for oxygen heating in the production of titanium dioxide (Ti02) - ethylene cracking tubes ' - furnace frames and supporting crosses for steady annealings - installations for exhaust manifolds - catalyst foils for waste gas purification, more particularly in the case of thermally heavily loaded small petrol engines, such as engines for chain saws, hedge clippers and lawn mowers.
The aforementioned articles can readily be produced from the material according to the invention, since it can not only be satisfactorily hot worked, but also has the necessary shaping capacity for cold working processes such as, for instance, cold rolling to thin dimensions, chamfering, deep drawing, flanging.
(Captions of drawings):
Fig. 1 = heat resistance Rm, details in MPa: Leg. = alloy;
Fig. 2 = 1o yield point Rp, details in MPa:
Fig. 3 = Z% time~yield point-Rpl.O/10000, details in MFa;
Fig. 4 = creep rupture strength Rm/10000, details in I~iPa;
Fig. 5 = cyclic resistance to oxidation in air, details in g/m2.ht (top left) specific change in weight in g/m2.h$
The heat resistance values are stated as follows 80 MPa for 1800°F, 45 MPa for 2000°F and 23 MPa for 2100°F.
After 1000 hours the creep rupture strength was 32 MPa for 1600°F, 16 MPa for 1800°F and 7 MPa for 2000°F. Material NiCr23Fe (Material No. 2.4851 and UNS Designation N 06601), which lies within these alloying limits, was introduced for industrial use on that basis. The material proves its usefulness above all when applied in the temperature range above 1000°C. This is due to the formation of a protective layer of chromium oxide-aluminium oxide, but more particularly to the overall low tendency of 'the oxide layer to peel. off under alternating temperature loadings. The material. has therefore been developed into an important material in industrial furnace construction.-Typical applications are radiation tubes for gas-heated furnaces and conveying rollers in roller hearth furnaces for ceramic products. Moreover, the rnaterial.is also suitable for parts of waste gas detoxification installations and petrochemical plants.
To further enhance the properties decisive for the use of this material for utilization temperatures above 1100 to 1200°C, according to US Patent Specification 4 784 830 nitrogen in quantities of 0.04 to 0.1o by weight are added to the material known from US Patent Specificat~.on 3 607 243, while at the same time a titanium content of 0.2 to l.Oa is compulsory.
Advantageously the silicon content should also be above 0.25% by weight and so correlated with the titanium content as to obtain a Si:Ti ratio of 0.85 to 3Ø The chromium contents are 19 - 23a, the aluminium contents being 0.75 - 2.00, with nickel contents of 55 - 65%.
By these steps an improvement in resistance to oxidation with utilization temperatures up to 1200°C is achieved, something which enabled the service life of, for example, furnace rollers to be increased to 12 months and more, in comparison with 2 months in the case of furnace rollers made from the material disclosed in US Patent Specification 3 607 243. This improvement in the service life of furnace components is mainly due to a stabilization of the microstructure by titanium nitrides at temperatures of 1200°C. As described in US Patent Specification 3 607 243, the carbon content also must not exceed 0.1% by weight, to prevent the formation of carbides, more particularly of the type M23C6, since these have a disadvantageous effect on microstructure and on the properties of the alloy at very high temperatures.
However, not only resistance to oxidation (expressed by cyclic change in weight (g/mZ.h) in air at high test temperatures, e.g., 2000'f, as described in US.Patent Specification 4 784 830) is decisive for the. service life-of highly heat-resistant particles, but so are resistance to heat and creep rupture strength at the particular temperatures of utilization.
Tt is an object of the invention so to design, nickel-chromium-iron alloys of the kind specified that, accompanied by adequate resistance to oxidation, the values of heat resistance and creep rupture strength are impro.v~d, thus significantly increasing the service life of articles made from such alloys.
This problem is solved by an austenitic nickel-chromium-iron.alloy, consisting of (details in % by weight):
carbon . 0.12 to 0.30 %
chromium . 23 to 30 %
iron . 8 to 11 aluminium . 1.8 to 2.4' yttrium . 0.01 to 0.15 %
titanium . 0.01 to 1.0 %
niobium . 0.01 to 1.0 zirconium . 0.01 to 0.20 magnesium . 0.001 to 0.015 %
calcium. . 0.001 to 0Ø10 nitrogen . max 0.030 silicon . max 0.50 %
manganese . max 0.25 phosphorus . max 0.020 sulphur . - max 0.010 4 nickel . residue , including unavoidable impurities caused by melting.
~n a preferred variant of the alloy, the contents are as.follows:
carbon . 0.15 to 0.25 chromium . 24 to 26 %
aluminium . 2.1 to 2.4 yttrium . 0.05 to 0.12 0 titanium . 0.40 to 0.60 0 ;
niobium . 0.40 to 0.60 0 zirconium . 0.01 to 0.10 0 nitrogen . max 0.010 %.
with, unaltered ranges of content the t of the alloying of res elements.
The nickel-chromium-iron alloy according to the invention has carbon contents of 0.12 to 0.3% by weight, in contrast with the prior art, which~permits carbon contents only up to 0.100 by weight at the most, since it was believed that only such low carbon contents could ensure the required existence to oxidation at temperatures up to 1200°C.
Surprisingly, carbon contents of this order of magnitude in conjunction with the other additives provided according to the invention, mare particularly yttrium and zirconium, not only enhance heat resistance and creep rupture strength, but also improve, resistance to oxidation.
Since in the alloy according to the invention the nitrogen content is kept~as low as possible, the carbon contents according.
to the invention of 0.1.2 to 0.30% by weight, in conjunction with the stable carbide formers titanium, niobium and zirconium, produce essentially carbides of said elements which are thermally stable even at temperatures up to 1200°C. As a result, the formation of chromium carbides of the type Cr2gC6 is substantially prevented thereby. The result is that in the first place, the formation of the titanium, niobium and zirconium CarDldeS . ~.JCll.~f? Slave gr°_3tSr t er_?la1 StaD111t'T t an t a C.
rOmi'.131 Car'JlQeS ~ aSt_:.:?g! j l~:l~Y'.~~VeS reSlSLanC2 t0 ~ea~ aI'lC Crr°O r '~~::~5 , Strength, While in the Second place more ChrOmlum is avail3Jle fOZ"tile formation Of a prOteCtl.Ve Chromium oxide layer, SO that resistance to oxidation is improved with the simultaneous addition of yttrium and airconium.
Chromium contents of at least 23% by weigzt are rec_r'.:i red to ensure adeauate resistance to oxidation at temperatures of above 1200°C. The top limit should not exceed 30% by weight, to avoid problems in the hot working of the alloy.
Particularly in the temperature range betTaeen 600 and 800°C, which the material when used passes through both during heating and also cooling, aluminium improves resistance to heat by the precipitation of the phase Ni3Al (so-called '~ ' phase) . Since the preCipltation of this phase is at the same time connected with a drop in toughness, the aluminium contents must be limited to 1.8 to 2.~~ by we~g~.t.
The silicon content should be as lcw as possible, to avoid the formation of low-melting phases. The manganese content should not exceed O.zS% by weigt?t,~ to avoid negative ez'fec~s on the resistance to oxidation of the material.
Additions of magnesium and calcium improve hat workability and also enhance resistance to oxidation. However, the top limits of 0.025% by weight (magnesium) and 0.020% by weight (oalcium) should not be exceeded, since~magnesium and calcium contents ' .oove these limit values encourage the occurrence of low-melting phases and therefore lead to a deterioration in hot workability.
The iron contents of the alloy according to the invention lie in the range of 8 to llo by weight, these values being determined by the need to be able to use cheap ferrochrome and ferronickel in the melting of the alloy.
The advantages achieved by the alloy according to the invention will be explained in detail hereinafter. Table 1 takes the analyses of two alloys A and B according to the invention and a prior art alloy C, such as can be gathered from US Patent Specification 4 784 830.
Table 1 Allay A Alloy B ~ Alloy C
(contents stated in o by weight) carbon 0.18 0.18. 0.055 chromium 25.0 25.5 23.0 iron 11.0 10.0 14.0 aluminium 1.85 ~ 2.10 1.35 yttrium 0.06 0.11 titanium 0.15 0.59 0.45 niobium 0.01 0.59 zirconium 0.10 0.10 magnesium 0.008 ~ O.OOE
calcium 0.002 O.OOI
nitrogen 0.002 0.006 0.040 _8_ ~~~4~~
silicon 0.29 0.06 0.40 manganese 0.15 0,02 0.25 phosphorus 0.004 0.003 0.011 sulphur 0.003 0.002 0.004 nickel residue residue residue The material properties of these alloys form the subaect matter of Figs. 1 to 5, which show:
Ficx~~ for the alloys A, B and C
heat resistance Rm (MPa) in dependence on temperature (°C) Fic~. 2 for the alloys A, B and C
the 1o yield point Rp (MPa) in dependence on temperature (°G) F_iq. 3 for the alloys A and C
the to time yield limit Rp 1.0/10000 (MPa) after a time of 10000 hours in dependence on temperature (°C) Fib. ~4 for the alloys A and C
the creep rupture strength in dependence on temperature Rm/10000 (MPa) after a time of 10000 hours in dependence on temperature (°), and Fig. 5 for the alloys A and C
the cyclic resistance to oxidation in air (specific change in weight in g/m2.h) in dependence on temperature.(°C).
"'he -values plotted in dependence or. temperature in Fia. 1 for heat resistance and i n Fi a. 2 for th a 1% yiel d poi:,t are important characteristic values, indicating the extent to which the material can be loaded at a particular temperature.
It must be pared that over the whole temperature range in question of 850 to 1.200°C, the alloy according to the invention has distinctly higher values than the prior art alloy C as regards both heat resistance Rm and also the to yield point Rp.
Bven better values are achieved by the alloy B according to the invention, whose composition lies within the variant alloy set forth in claim 2. By this variant alloy both the heat resistance and also the yield point can be almost doubled up to temperatures of 1000 ° C.
Fia. 3 and Fia. 4 compare the creep rupture strength behaviour of the alloy A according to the invention with that of the prior art alloy C.
The creep rupture strength and the l~ time yield point were determined in the usual creep tests (cf. "Wet~kstoffkunde Stahl°', Vol. l, published by Springer Verlag, Berlin, 2984, pages 384 to 396 and DIN 5011.8).
Creep rupture strength (MFa) is taken to be a measurement of the capability of the material not to be destroyed by the effect of an operative load. The 1°s time yield point, which states the stress (in MPa) far a given loading time at which a to expax~sion is reached, characterizes the functional failure of material at a particular long-term loading for the 'temperature in question.
The alloy A according to the invention is clearly superior to the prior art alloy C over the whole temperature range both as regards creep rupture strength and also the 1o time yield point.
In comparison with the alloy C, the gain in strength of the alloy A according to the invention is more than 25~ at every temperature.
In Fib. 5 the cyclic resistance to oxidation determined in air for the alloys A and C are compared by plotting specific change in weight over temperature. As a rule increases in.weight (+) are desirable, since reductions in weight (-) are often an indication of heavily peeling scale.
For this reason the behaviour of the alloy A according to the invention must be considered superior to that of the prior art' alloy C, which intersects the abscissa (transition to loss in weight) as early as about 1000°C, while the alloy A passes through zero only at approximately 1050°C.
Due to its satisfactory properties at elevated temperatures, the nic3sel-chromium-iron alloy according to the invention is a preferred material for articles which must have a creep rupture strength (Rm/10000) of at least 5 MPa, accompanied by a la time yield paint (Rpl.O/10000) of at least 2 MPa and high resistance to oxidation in practical operation, referred to a temperature of 7.100°C and a loading duration of 10000 hours, such as, for examples - radiation tubes for the heating of furnaces - furnace rollers for the annealing of metal ox ceramic goads ~~~~4~~
- muffles for scaling furnaces, for example, for furnaces for the bright annealing of special quality steels - tubes for oxygen heating in the production of titanium dioxide (Ti02) - ethylene cracking tubes ' - furnace frames and supporting crosses for steady annealings - installations for exhaust manifolds - catalyst foils for waste gas purification, more particularly in the case of thermally heavily loaded small petrol engines, such as engines for chain saws, hedge clippers and lawn mowers.
The aforementioned articles can readily be produced from the material according to the invention, since it can not only be satisfactorily hot worked, but also has the necessary shaping capacity for cold working processes such as, for instance, cold rolling to thin dimensions, chamfering, deep drawing, flanging.
(Captions of drawings):
Fig. 1 = heat resistance Rm, details in MPa: Leg. = alloy;
Fig. 2 = 1o yield point Rp, details in MPa:
Fig. 3 = Z% time~yield point-Rpl.O/10000, details in MFa;
Fig. 4 = creep rupture strength Rm/10000, details in I~iPa;
Fig. 5 = cyclic resistance to oxidation in air, details in g/m2.ht (top left) specific change in weight in g/m2.h$
Claims (3)
1. An austenitic nickel-chromium-iron alloy consisting of (details in % by weight):
carbon : 0.12 to 0.30 %
chromium : 23 to 30 %
iron : 8 to 11 %
aluminium : 1.8 to 2.4 %
yttrium : 0.01 to 0.15 %
titanium : 0.01 to 1.0 %
niobium : 0.01 to 1.0 %
zirconium : 0.01 to 0.20 %
magnesium : 0.001 to 0.015 %
calcium : 0.001 to 0.010 %
nitrogen : max 0.030 %
silicon : max 0.50 %
manganese : max 0.25 %
phosphorus : max 0.020 %
sulphur : max 0.010 %
nickel : residue including unavoidable impurities caused by melting.
carbon : 0.12 to 0.30 %
chromium : 23 to 30 %
iron : 8 to 11 %
aluminium : 1.8 to 2.4 %
yttrium : 0.01 to 0.15 %
titanium : 0.01 to 1.0 %
niobium : 0.01 to 1.0 %
zirconium : 0.01 to 0.20 %
magnesium : 0.001 to 0.015 %
calcium : 0.001 to 0.010 %
nitrogen : max 0.030 %
silicon : max 0.50 %
manganese : max 0.25 %
phosphorus : max 0.020 %
sulphur : max 0.010 %
nickel : residue including unavoidable impurities caused by melting.
2. An austenitic nickel-chromium-iron alloy according to claim 1, having the following contents:
carbon : 0.15 to 0.25 %
chromium : 24 to 26 %
aluminium : 2.1 to 2.4 %
yttrium : 0.05 to 0.12 %
titanium : 0.40 to 0.60 %
niobium : 0.40 to 0.60 %
zirconium : 0.01 to 0.10 %
nitrogen : max to 0.010 0%.
carbon : 0.15 to 0.25 %
chromium : 24 to 26 %
aluminium : 2.1 to 2.4 %
yttrium : 0.05 to 0.12 %
titanium : 0.40 to 0.60 %
niobium : 0.40 to 0.60 %
zirconium : 0.01 to 0.10 %
nitrogen : max to 0.010 0%.
3. Use of an austenitic nickel-chromium-iron alloy according to one of claims 1 or 2 as a material for articles heavily thermally loaded in practical operation which, referred to a temperature of 1100°C and a duration of loading of 10000 hours, must have a creep rupture strength (Rm/10000) of at least 5 MPa with a 1%
time yield limit (Rp1.0/10000) of at least 2 MPa and a high resistance to oxidation.
time yield limit (Rp1.0/10000) of at least 2 MPa and a high resistance to oxidation.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4111821A DE4111821C1 (en) | 1991-04-11 | 1991-04-11 | |
| DEP4111821.9-24 | 1991-04-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2065464A1 CA2065464A1 (en) | 1992-10-12 |
| CA2065464C true CA2065464C (en) | 2002-03-26 |
Family
ID=6429356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002065464A Expired - Lifetime CA2065464C (en) | 1991-04-11 | 1992-04-07 | Austenitic nickel-chromium-iron alloy |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5980821A (en) |
| EP (1) | EP0508058B1 (en) |
| JP (1) | JP3066996B2 (en) |
| AT (1) | ATE126548T1 (en) |
| AU (1) | AU653801B2 (en) |
| CA (1) | CA2065464C (en) |
| DE (2) | DE4111821C1 (en) |
| ES (1) | ES2079705T3 (en) |
Families Citing this family (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2073873T3 (en) * | 1991-12-20 | 1995-08-16 | Inco Alloys Ltd | NI-CR ALLOY WITH HIGH TEMPERATURE RESISTANCE. |
| DE19524234C1 (en) * | 1995-07-04 | 1997-08-28 | Krupp Vdm Gmbh | Kneadable nickel alloy |
| RU2131943C1 (en) * | 1997-03-05 | 1999-06-20 | Открытое акционерное общество "Всероссийский институт легких сплавов" | Nickel-base heat-resistant alloy |
| DE19753539C2 (en) * | 1997-12-03 | 2000-06-21 | Krupp Vdm Gmbh | Highly heat-resistant, oxidation-resistant kneadable nickel alloy |
| US5997809A (en) * | 1998-12-08 | 1999-12-07 | Inco Alloys International, Inc. | Alloys for high temperature service in aggressive environments |
| GB2361933A (en) * | 2000-05-06 | 2001-11-07 | British Nuclear Fuels Plc | Melting crucible made from a nickel-based alloy |
| WO2002076669A1 (en) * | 2001-03-23 | 2002-10-03 | Citizen Watch Co., Ltd. | Brazing filler metal |
| US6488783B1 (en) * | 2001-03-30 | 2002-12-03 | Babcock & Wilcox Canada, Ltd. | High temperature gaseous oxidation for passivation of austenitic alloys |
| JP3998983B2 (en) | 2002-01-17 | 2007-10-31 | 松下電器産業株式会社 | Unicast-multicast converter and video surveillance system |
| RU2220220C1 (en) * | 2002-08-05 | 2003-12-27 | Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" | High-temperature nickel alloy, article made out of this alloy, method of thermal treatment of alloy and article out of this alloy |
| DE10302989B4 (en) | 2003-01-25 | 2005-03-03 | Schmidt + Clemens Gmbh & Co. Kg | Use of a heat and corrosion resistant nickel-chromium steel alloy |
| EP1610081A1 (en) * | 2004-06-25 | 2005-12-28 | Haldor Topsoe A/S | Heat exchange process and heat exchanger |
| ES2671703T3 (en) * | 2007-10-05 | 2018-06-08 | Sandvik Intellectual Property Ab | A steel reinforced by dispersion as a material roller for a roller hearth furnace |
| US8506883B2 (en) * | 2007-12-12 | 2013-08-13 | Haynes International, Inc. | Weldable oxidation resistant nickel-iron-chromium-aluminum alloy |
| US9551051B2 (en) | 2007-12-12 | 2017-01-24 | Haynes International, Inc. | Weldable oxidation resistant nickel-iron-chromium aluminum alloy |
| DE102012013437B3 (en) | 2011-02-23 | 2014-07-24 | VDM Metals GmbH | Use of a nickel-chromium-iron-aluminum alloy with good processability |
| DE102012011162B4 (en) | 2012-06-05 | 2014-05-22 | Outokumpu Vdm Gmbh | Nickel-chromium alloy with good processability, creep resistance and corrosion resistance |
| DE102012011161B4 (en) | 2012-06-05 | 2014-06-18 | Outokumpu Vdm Gmbh | Nickel-chromium-aluminum alloy with good processability, creep resistance and corrosion resistance |
| JP5857894B2 (en) * | 2012-07-05 | 2016-02-10 | 新日鐵住金株式会社 | Austenitic heat-resistant alloy |
| DE102012015828B4 (en) * | 2012-08-10 | 2014-09-18 | VDM Metals GmbH | Use of a nickel-chromium-iron-aluminum alloy with good processability |
| DE102014001329B4 (en) | 2014-02-04 | 2016-04-28 | VDM Metals GmbH | Use of a thermosetting nickel-chromium-titanium-aluminum alloy with good wear resistance, creep resistance, corrosion resistance and processability |
| DE102014001330B4 (en) | 2014-02-04 | 2016-05-12 | VDM Metals GmbH | Curing nickel-chromium-cobalt-titanium-aluminum alloy with good wear resistance, creep resistance, corrosion resistance and processability |
| DE102018107248A1 (en) | 2018-03-27 | 2019-10-02 | Vdm Metals International Gmbh | USE OF NICKEL CHROME IRON ALUMINUM ALLOY |
| WO2020126053A1 (en) * | 2018-12-21 | 2020-06-25 | Sandvik Intellectual Property Ab | New use of a nickel-based alloy |
| DE102020132193A1 (en) * | 2019-12-06 | 2021-06-10 | Vdm Metals International Gmbh | Use of a nickel-chromium-iron-aluminum alloy with good workability, creep resistance and corrosion resistance |
| DE102020132219A1 (en) | 2019-12-06 | 2021-06-10 | Vdm Metals International Gmbh | Use of a nickel-chromium-aluminum alloy with good workability, creep resistance and corrosion resistance |
| DE102022105658A1 (en) | 2022-03-10 | 2023-09-14 | Vdm Metals International Gmbh | Process for producing a component from the semi-finished product of a nickel-chromium-aluminum alloy |
| DE102022105659A1 (en) | 2022-03-10 | 2023-09-14 | Vdm Metals International Gmbh | Process for producing a welded component from a nickel-chromium-aluminum alloy |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB810366A (en) * | 1957-09-25 | 1959-03-11 | Mond Nickel Co Ltd | Improvements relating to heat-resisting alloys |
| US3607243A (en) * | 1970-01-26 | 1971-09-21 | Int Nickel Co | Corrosion resistant nickel-chromium-iron alloy |
| JPS5953663A (en) * | 1982-09-22 | 1984-03-28 | Kubota Ltd | Heat-resistant cast steel with superior carburization resistance and superior creep rupture strength at high temperature |
| JPS6179742A (en) * | 1984-09-26 | 1986-04-23 | Mitsubishi Heavy Ind Ltd | Heat resistant alloy |
| US4784830A (en) * | 1986-07-03 | 1988-11-15 | Inco Alloys International, Inc. | High nickel chromium alloy |
| CA1304608C (en) * | 1986-07-03 | 1992-07-07 | Inco Alloys International, Inc. | High nickel chromium alloy |
| US5217684A (en) * | 1986-11-28 | 1993-06-08 | Sumitomo Metal Industries, Ltd. | Precipitation-hardening-type Ni-base alloy exhibiting improved corrosion resistance |
| JPH0660369B2 (en) * | 1988-04-11 | 1994-08-10 | 新日本製鐵株式会社 | Cr-Ni type stainless steel that is less likely to crack during the casting process or the subsequent hot rolling process |
-
1991
- 1991-04-11 DE DE4111821A patent/DE4111821C1/de not_active Expired - Fee Related
-
1992
- 1992-02-11 DE DE59203257T patent/DE59203257D1/en not_active Expired - Lifetime
- 1992-02-11 EP EP92102228A patent/EP0508058B1/en not_active Expired - Lifetime
- 1992-02-11 ES ES92102228T patent/ES2079705T3/en not_active Expired - Lifetime
- 1992-02-11 AT AT92102228T patent/ATE126548T1/en active
- 1992-04-02 US US07/862,486 patent/US5980821A/en not_active Expired - Lifetime
- 1992-04-07 CA CA002065464A patent/CA2065464C/en not_active Expired - Lifetime
- 1992-04-08 AU AU14787/92A patent/AU653801B2/en not_active Expired
- 1992-04-13 JP JP4092718A patent/JP3066996B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| AU1478792A (en) | 1992-10-15 |
| US5980821A (en) | 1999-11-09 |
| EP0508058B1 (en) | 1995-08-16 |
| ES2079705T3 (en) | 1996-01-16 |
| AU653801B2 (en) | 1994-10-13 |
| JPH07216483A (en) | 1995-08-15 |
| ATE126548T1 (en) | 1995-09-15 |
| EP0508058A1 (en) | 1992-10-14 |
| DE59203257D1 (en) | 1995-09-21 |
| DE4111821C1 (en) | 1991-11-28 |
| CA2065464A1 (en) | 1992-10-12 |
| JP3066996B2 (en) | 2000-07-17 |
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